EP0001371B1 - Verfahren zur Enthalogenierung von aromatischen Halogenverbindungen - Google Patents

Verfahren zur Enthalogenierung von aromatischen Halogenverbindungen Download PDF

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Publication number
EP0001371B1
EP0001371B1 EP78420008A EP78420008A EP0001371B1 EP 0001371 B1 EP0001371 B1 EP 0001371B1 EP 78420008 A EP78420008 A EP 78420008A EP 78420008 A EP78420008 A EP 78420008A EP 0001371 B1 EP0001371 B1 EP 0001371B1
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Prior art keywords
support
process according
metal
alumina
salt
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Expired
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EP78420008A
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French (fr)
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EP0001371A1 (de
Inventor
Georges Biola
Jean Font
Jean-Claude Daumas
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Bayer CropScience SA
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Rhone Poulenc Agrochimie SA
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals

Definitions

  • the present invention relates to a process for the manufacture of halogenated aromatic compounds by dehalogenation of corresponding derivatives carrying a greater number of halogen atoms. It more specifically relates to the manufacture of metasubstituted chloro-anilines, in particular 3,5-dichloro aniline from more highly chlorinated anilines.
  • 3,5-dichloro aniline can be obtained, according to French application 2162782, by a process of dehalogenation of halogenated aromatic compounds leading to the preferential production of derivatives carrying a lower number of halogen atoms, of which at least one is located in the meta position relative to a functional group, in the vapor phase, by the action of hydrogen and in the presence of catalysts in a fixed or fluidized bed, which is characterized in that it is brought into contact polyhalogenated aromatic amines or the corresponding nitro derivatives with hydrogen at a temperature between 280 and 420 ° C, in the presence of a hydrogenation catalyst with controlled action, such as a salt (chloride, oxide, nitrate, sulfate or chromite) of copper or silver.
  • a hydrogenation catalyst with controlled action such as a salt (chloride, oxide, nitrate, sulfate or chromite) of copper or silver.
  • This process is characterized by its improved selectivity in aromatic derivatives substituted in the meta position.
  • experience shows that it has the major drawback, in particular when using copper compounds on an alumina support, of requiring frequent regenerations of the catalyst as a result of the in situ formation of carbon deposits due the complete degradation of part of the reagents.
  • the present invention therefore relates to a process for the dehalogenation of halogenated, amino or nitrated aromatic compounds, leading to the preferential production of derivatives carrying a lower number of halogen atoms, at least one of which is substituted in meta position with respect to to the amino or nitro group, in the vapor phase, by the action, at a temperature between 280 and 420 ° C, of hydrogen in the presence of a mild-action hydrogenation catalyst deposited on a support based on alumina, characterized in that a support modified at least at the surface is used by incorporating a metal in the form of a salt or an oxide, this incorporation comprising a treatment of the support with said salt or metal oxide followed by calcination at a temperature ranging from about 500 to 1000 ° C.
  • This support thus modified contains from 0.2 to 30% and preferably from 5 to 20% by weight of metal incorporated with respect to the initial support.
  • the support which can be used according to the invention is usually in the form of silica grains of fine particle size, that is to say of average diameter ranging from approximately 60 to 200, and preferably approximately 80 to 100 microns, in the case of fluidized beds or of larger particle size, of the order of a few millimeters, in the case of fixed beds.
  • the specific surface area of the grains is generally between approximately 20 and 500 m 2 / g and preferably 60 to 300 m 2 / g.
  • the first phase of incorporating the metal into the support can be carried out according to several variants.
  • the first consists of impregnating the support with a solution of an alkali metal salt, alkaline earth metal or metal with several valences.
  • This technique is particularly suitable for alumina-based supports, this combining with the impregnation salt after calcination, to give either aluminates or solid alumina / metal oxide solutions.
  • iron, nickel, cobalt, zinc and copper as well as chromium, molybdenum or tungsten can be used advantageously. According to this technique, good results have been obtained with magnesium, copper and chromium oxide salts.
  • the second variant consists in incorporating the metal according to a sol-gel technique, by mixing a metal salt and an aluminum salt, gelation, by neutralization with hexamethylene tetramine, of the resulting compound with dispersion in fine droplets in a hot hydrocarbon, the latter taking a spheroidal shape.
  • alumina sol is understood to mean in particular any basic aluminum salt of general formula AI2 (OH) 6-a X a in which X is at least one of the anions chosen from the group consisting of halides NOg ", C10 4 -; aluminum hydrochlorides are preferred.
  • These basic aluminum salts can be obtained in particular by digestion of metallic aluminum in HX acid or in a solution of AIX 3 , by electrolysis of a aluminum salt solution, by neutralization of a more or less basic aluminum salt with a base and elimination of the salt formed, by reaction of an aluminum salt, by neutralization of an aluminum salt more or less basic by a base and elimination of the salt formed, by reaction of an aluminum salt with a donor electrons such as ethylene oxide and elimination of the reaction product, by bringing an aluminum salt into contact with a water-immiscible solvent containing a long chain aliphatic amine then recovery of the aqueous phase containing the basic salt and concentration, by peptization of a freshly precipitated alumina gel, by attack of an aluminum oxide or hydroxide with HX acid.
  • the alumina sol solution contains from 5 to 35% by weight of alumina counted as AI 2 0 3 and has an atomic ratio AI / X of between 1.33 and 2.67. According to a preferred implementation, the concentration of alumina in the solution of the starting sol is between 15 and 30% by weight and the atomic ratio AI / X is between 1.60 and 2.20.
  • the concentration of the hexamethylenetetramine solution used according to the invention is between 15 and 45% by weight, according to a preferred implementation, it is approximately 30 to 45% by weight.
  • the hexamethylenetetramine solution is intimately mixed with the alumina sol solution at a temperature below the gelling temperature of the mixture.
  • This mixture is carried out in volume ratios of hexamethylenetetetramine-alumina sol of between 3: 1 and 1:20 approximately, the value of this ratio depending in particular on the alumina concentration and on the value of the atomic ratio AI / X of the starting soil, it may be advantageous to carry out the mixing in proportions such that these volume ratios are between 1: 1 and 1: 6.
  • liquids which are hardly miscible with water petroleum, kerosene, dodecylbenzene, alcohols and organic solvents in general.
  • the mixture droplets gel due to the neutralization of the anions contained in the starting soil by the ammonia released during the hydrolysis of hexamethylene tetramine.
  • the aluminum concentration of the mixture is between 6 and 12% by weight, and preferably between 7 and 11%, than, moreover, the hexamethylene-tetramine / chlorine molar ratio is greater than 0.17 and preferably between 0.2 and 0.6, that the temperature of the forming liquid is between 50 and 150 ° C, and preferably between 85 and 95 ° C, and that the residence time in the forming medium is between 1 second and 2 hours approximately.
  • the beads obtained are aged in the same type of medium very little miscible with water as the forming medium.
  • This aging is carried out at a temperature below 130 ° C and preferably between 100 and 110 ° C and under a pressure higher than atmospheric pressure and for which the water contained in the gel spheres is kept in the state liquid. It may be advantageous to carry out this aging at a temperature between 120 and 150 ° C. and for a period of 10 to 30 hours and preferably from 16 to 24 hours.
  • This technique is particularly suitable for the incorporation of chromium oxide in alumina supports. Microbeads are thus obtained, after calcination, which have, with respect to the alumina support in which chromium oxide has been incorporated according to the first variant, that is to say by impregnation, more homogeneous presentation and higher mechanical resistance with, as a consequence, an increase in the performance and durability of the catalyst assembly.
  • the treated support is then calcined at a temperature ranging from 500 to 1000 ° C. and preferably from 800 to 1000 ° C.
  • the support thus modified is impregnated in a manner known per se with a salt (chloride, sulphate, nitrate, chromite) or oxide of a metal with properties of hydrogenation catalyst with controlled action, such as for example silver and preferably copper, but other catalysts or catalytic combinations of hydrogenation with an efficiency comparable to the salt of the abovementioned metals can also be envisaged.
  • a salt chloride, sulphate, nitrate, chromite
  • oxide of a metal with properties of hydrogenation catalyst with controlled action such as for example silver and preferably copper, but other catalysts or catalytic combinations of hydrogenation with an efficiency comparable to the salt of the abovementioned metals can also be envisaged.
  • One of the advantages of the process also lies in the fact that it makes it possible to make use of certain polyhalogenated compounds, in particular polychlorinated compounds, which do not in themselves have an extensive application: this is how, for example, certain isomers of tri- and tetrachlor-benzenes which are little used, and of a low price of returns, can be converted into tri and tetrachloranilines which allow to lead, according to the method according to the invention, to a compound such as dichloro-3,5 aniline; the latter is then manufactured under economically much more advantageous conditions than when it is prepared according to the method known to date.
  • Another interesting example concerns certain dichloranilines, one of the chlorines of which is in the meta position, in particular 3-dichloro aniline.
  • the temperature is a fairly important factor and must be maintained in the range of 280 to 420 ° C., if one wishes to operate in the gas phase of the starting halogenated aromatic derivatives and obtain the desired selectivity and a suitable conversion rate without sensitive formation of undesirable products, in particular by degradation, cracking. Within these limits, the more specially adapted temperature range is a function of various variables. First of all, silver-based catalysts generally require a relatively high range, of the order of 250 to 420 ° C., while those based on copper admit the lower temperature range as well, within the limits of l 'invention. We can also play on this factor to modify the relative proportions of finished products.
  • the quantity of hydrogen to be brought into play in the process of the invention does not constitute a determining factor and can represent, at will, the stoichiometric proportion, relative to the number of halogen atoms to be eliminated, or preferably a small or large excess.
  • the reaction takes place easily, is very rapid, at most of the order of a few seconders or even fractions of a second, and adapts perfectly to atmospheric pressure, although the application of a lower or higher pressure is obviously not not excluded.
  • the starting polyhalogenated aromatic amines are prepared in situ by introducing into the dehalogenation zone the polyhalogenated aromatic nitro compounds used to obtain said amines: the conversion of the nitro derivatives to anilines is very high, even quantitative.
  • the desired amines which are relatively little halogenated, can be produced in a single stage directly from nitro compounds carrying a greater number of halogen atoms.
  • An example of such a procedure is, in particular, the manufacture of 3,5-dichloro aniline from 1-nitro-2,3,4,5-tetrachlor or 2,3-nitro-tetrachloro-2,3,5,6 benzene or pentachloronitrobenzene.
  • a convenient means of implementing the process according to the invention consists in introducing hydrogen and the halogenated raw material, previously vaporized, from the bottom of a reaction zone containing a catalytic bed consisting of support particles on which is deposited the catalyst, and brought to the reaction temperature, which is kept substantially constant. It is possible, by suitably regulating the gas introduction rate, to maintain the catalytic bed in the fluidized state. It is advantageous to quickly eliminate the products formed from the dehalogenation zone in order to avoid secondary reactions and degradation phenomena.
  • the gaseous effluent contains the halogen-hydric gas formed during the reaction, generally hydrogen and unprocessed raw material, and the aromatic compounds resulting from dehalogenation, the major proportion of which is represented by derivatives carrying halogen in the meta position, while the rest contains various halogenated isomers and, where appropriate, a small proportion of non-halogenated product and various impurities; these amines are present at least partially in the form of halohydrates.
  • This mixture is treated, with a view to the separation of its constituents, by application of various techniques.
  • An advantageous means consists in first putting the gaseous effluent resulting from the reaction in contact with a liquid or a vapor, such as an aliphatic alcohol such as methanol, a hydrocarbon such as benzene, or water. , being at a temperature significantly lower than said effluent, for example at 100 ° C. or less depending on the compound involved, in order to rapidly condense the anilines and / or their halohydrates.
  • the various amino compounds are then separated, for example by crystallization. Amines can be recovered in the free state if necessary, by the application of conventional methods such as treatment with a basic compound such as sodium hydroxide, potassium hydroxide, an alkali carbonate, etc.
  • the amines can also be released first, then separated by crystallization or distillation. If water is used in this technique, it also takes advantage of the fact that certain amine halohydrates are insoluble in an aqueous medium, while others are soluble. Thus, for example, the hydrochlorides of tri- and tetrachloranilines are practically insoluble, while those of mono and dichloranilines are soluble. An aqueous solution is then collected in which the halohydrous gas and certain aniline halohydrates are dissolved and which contains, in suspension or in the form of precipitates, the insoluble halohydrates. By a simple physical or mechanical operation, such as filtration or centrifugation, there is then obtained a separation between soluble or insoluble products. The solid phase and the soluble phase are then treated separately as indicated above, to isolate the amino compounds.
  • the untransformed starting amine or haloamines resulting from the reaction but not specially sought after - for example, the trihalogenated derivatives in the case of a production essentially targeting dihalogenated derivatives - can advantageously be recycled wholly or in part, in the reaction zone, where they are again subjected to the dehalogenation process according to the invention. Recycling can be carried out either with the halohydrates or with the free amines.
  • 100 g of flash alumina grains (size 20 to 100 microns) having a specific surface of 300 m l / g are impregnated with an aqueous solution of magnesium nitrate Mg (NO 3 ) 2 .6H 2 O, so as to obtain a final content of 5% by weight of magnesium relative to the finished catalyst (or approximately 5.25% by weight relative to the support).
  • the impregnated support is then calcined at 950 ° C. for 3 hours.
  • the operation is carried out in the same way on another alumina sample similar to the first, but by impregnating with an aqueous solution of chromium oxide (Cr0 3 ) so as to obtain a final chromium content of 10% by weight. (or about 11.1% by weight relative to the support).
  • the impregnated support is then calcined under the same conditions as above.
  • the catalyst is then prepared, according to a conventional technique, by impregnating the modified support with a cupric chloride solution so as to obtain a final copper content of 6% by weight relative to the "support-active phase" set (approximately 6.4% compared to the support modified or not).
  • the impregnated support is then dried at 200 ° C.
  • the particle size distribution of the droplets formed can be adjusted as desired. These coagulate in hot oil taking the spherical shape.
  • the microbeads After heating for 21 hours at 100 ° C in the petroleum bath, the microbeads are separated, washed with water, dried for 12 hours at 100 ° C and then calcined for 4 hours at 900 ° C to give rise to the formation of a solid solution "chromium-alumina oxide".
  • This support is then impregnated using a solution of copper chloride by a conventional technique (bezel) and then dried at 200 ° C.
  • the catalyst obtained containing 10% chromium and 6% copper will be designated by 3.
  • the contact time of the gas mixture with the catalyst is 3 seconds. The whole operation takes around 4 hours. From the top of the dehalogenation zone, the reaction effluent passes through a water washing column; this entrains the anilines and HCI while the excess hydrogen is rejected to the atmosphere. The mass recovered at the bottom of the washing column is then neutralized with sodium hydroxide in order to release the organic part which is analyzed by vapor phase chromatography and thin layer chromatography.
  • Example 3 One operates as in Example 3 with the catalyst 2, except that is introduced into the reactor an equal volume of 3,4-dichloro vaporized aniline and hydrogen in a molar ratio H 2/3 , 4-DCA equal to about 5.
  • the reaction is carried out for 3 hours at 320 ° C with a residence time of 3 seconds.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (11)

1. Verfahren zur Enthalogenierung von halogenierten aromatischen Aminen unter vorzugsweiser Erzielung von Derivaten mit einer geringeren Halogenatomanzahl, wovon wenigstens eines in Metastellung bezüglich der Aminogruppe substituiert ist, in der Dampfphase, durch Einwirkung von Wasserstoff bei einer Temperatur zwischen 280 und 420°C in Gegenwart eines metallischen Hydrierungskatalysators mit schonender Wirkung, der aus der Gruppe bestehend aus Kupfer und Silber ausgewählt und auf einem Trager aus Basisvon Aluminiumoxid abgelagert ist, dadurch gekennzeichnet, daß man einen Träger verwendet, der wenigstens an der Oberfläche modifiziert ist, durch Einverleibung eines Metalls in Form eines Salzes oder Oxids, wobei diese Einverleibung eine Behandlung des Trägers mit diesem Metallsalz oder Metalloxid und anschließende Kalzinierung bei einer Temperatur von etwa 500 bis 1000°C umfaßt.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man einen derart modifizierten Träger verwendet, der 0,2 bis 30 Gewichts-% einverleibtes Metall bezogen auf den ursprünglichen Träger enthält.
3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß man einen derart modifizierten Träger verwendet, der 5 bis 20 Gewicht-% einverleibtes Metall bezogen auf den ursprünglichen Träger enthält.
4. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man ein Metall einverleibt, ausgewählt aus der Gruppe bestehend aus den Alkali- und Erdalkalimetallen, Eisen, Nickel, Kobalt, Zink und Kupfer, sowie Chrom, Molybdän oder Wolfram.
5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, daß das in den Träger einverleibte Metall Magnesium ist.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Behandlung des Trägers mit dem Metallsalz oder Metalloxid durch Imprägnieren des Aluminiumoxids mit diesem Metallsalz oder Metalloxid bewirkt wird.
7. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Behandlung des Trägers mit dem Metallsalz oder Metalloxid bewirkt wird durch Vermischen eines Aluminiumsalzes mit einem Metallsalz, Gestaltung Gelierung durch Neutralisation der enstandenen Verbindung unter Dispergieren in einem heißen Kohlenwasserstoff zu feinen sphäriodalen Tröpfchen.
8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Kalzinierung des behandelten Trägers bei einer Temperatur von etwa 800 bis 1000°C bewirkt wird.
9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die polyhalogenierten aromatischen Ausgangsamine Aniline sind, die am Phenylring di-, tri-oder tetrahalogeniert sind.
10. Verfahren gemäß Anspruch 9, dadurch gekennzeichnet, daß die Halogenatome Chloratome sind.
11. Verfahren gemäß den Ansprüchen 1 bis. 10, dadurch gekennzeichnet, daß man die polyhalogenierten aromatischen Ausgangsamine in situ herstellt, indem man die polyhalogenierten nitrierten aromatischen Verbindungen, welche zur Erzeilung dieser Amine dienen, in die Enthalogenierungszone einführt.
EP78420008A 1977-09-22 1978-09-20 Verfahren zur Enthalogenierung von aromatischen Halogenverbindungen Expired EP0001371B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR7729400A FR2403991A1 (fr) 1977-09-22 1977-09-22 Procede de deshalogenation d'amines aromatiques halogenees
FR7729400 1977-09-22

Publications (2)

Publication Number Publication Date
EP0001371A1 EP0001371A1 (de) 1979-04-04
EP0001371B1 true EP0001371B1 (de) 1980-10-01

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EP78420008A Expired EP0001371B1 (de) 1977-09-22 1978-09-20 Verfahren zur Enthalogenierung von aromatischen Halogenverbindungen

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US (1) US4206148A (de)
EP (1) EP0001371B1 (de)
JP (1) JPS5838420B2 (de)
AT (1) AT361903B (de)
BR (1) BR7806158A (de)
CA (1) CA1130263A (de)
DD (1) DD139357A5 (de)
DK (1) DK419478A (de)
ES (1) ES473536A1 (de)
FR (1) FR2403991A1 (de)
GB (1) GB2005262B (de)
HU (1) HU184666B (de)
IE (1) IE47443B1 (de)
IL (1) IL55617A (de)
IT (1) IT1099601B (de)
SU (1) SU919591A3 (de)

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FR2774606B1 (fr) * 1998-02-11 2000-03-17 Rhodia Chimie Sa Procede d'elimination de composes halogenes contenus dans un gaz ou un liquide
US6589494B1 (en) 1998-03-31 2003-07-08 Institut Francais Du Petrole Process for eliminating halogen-containing compounds contained in a gas or liquid using an adsorbent composition based on at least one metallic element
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FR2403991B1 (de) 1981-01-30
JPS5838420B2 (ja) 1983-08-23
IT1099601B (it) 1985-09-18
US4206148A (en) 1980-06-03
ES473536A1 (es) 1979-05-16
GB2005262B (en) 1982-05-26
FR2403991A1 (fr) 1979-04-20
ATA683878A (de) 1980-09-15
DK419478A (da) 1979-03-23
HU184666B (en) 1984-09-28
DD139357A5 (de) 1979-12-27
AT361903B (de) 1981-04-10
IE781901L (en) 1979-03-22
BR7806158A (pt) 1979-04-17
EP0001371A1 (de) 1979-04-04
CA1130263A (en) 1982-08-24
GB2005262A (en) 1979-04-19
IT7828007A0 (it) 1978-09-22
IL55617A (en) 1982-01-31
IL55617A0 (en) 1978-12-17
IE47443B1 (en) 1984-03-21
JPS5455526A (en) 1979-05-02
SU919591A3 (ru) 1982-04-07

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